Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Visible-Light Controlled Divergent Catalysis Using a Bench-Stable Cobalt(I) Hydride Complex.

ABSTRACT: While the use of visible light in conjunction with transition metal catalysis offers powerful opportunities to switch between on/-off states of catalytic activity, the next frontier would be the ability to switch the actual function of the catalyst and resulting products. Here we report such an example of multi-dimensional catalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can switch the reaction outcome between two widely employed transformations, olefin migration and hydroboration, with visible light as the trigger.

SUBMITTER: Bergamaschi E

PROVIDER: S-EPMC7217149 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Visible-Light Controlled Divergent Catalysis Using a Bench-Stable Cobalt(I) Hydride Complex.

Bergamaschi Enrico E Beltran Frédéric F Teskey Christopher J CJ

Chemistry (Weinheim an der Bergstrasse, Germany) 20200325 23

While the use of visible light in conjunction with transition metal catalysis offers powerful opportunities to switch between on/-off states of catalytic activity, the next frontier would be the ability to switch the actual function of the catalyst and resulting products. Here we report such an example of multi-dimensional catalysis. Featuring an easily prepared, bench-stable cobalt(I) hydride complex in conjunction with pinacolborane, we can switch the reaction outcome between two widely employ ...[more]

PMID: 32027425

Similar Datasets

Controllable Isomerization of Alkenes by Dual Visible-Light-Cobalt Catalysis.

Project description:We report herein that thermodynamic and kinetic isomerization of alkenes can be accomplished by the combination of visible light with Co catalysis. Utilizing Xantphos as the ligand, the most stable isomers are obtained, while isomerizing terminal alkenes over one position can be selectively controlled by using DPEphos as the ligand. The presence of the donor-acceptor dye 4CzIPN accelerates the reaction further. Transformation of exocyclic alkenes into the corresponding endocyclic products could be efficiently realized by using 4CzIPN and Co(acac)2 in the absence of any additional ligands. Spectroscopic and spectroelectrochemical investigations indicate CoI being involved in the generation of a Co hydride, which subsequently adds to alkenes initiating the isomerization.

| S-EPMC6519376 | biostudies-literature

Visible-light photoredox catalysis in flow.

Project description: Not available

| S-EPMC3496249 | biostudies-literature

Synthesis of (±)-Tetrabenazine by Visible Light Photoredox Catalysis.

Project description:(±)-Tetrabenazine was synthesized in six steps from commercially available compounds. The key cyclization substrate was assembled rapidly via Baylis-Hillman and aza-Michael reactions. Annulation of the final ring was achieved through visible light photocatalysis, wherein carbon-carbon bond formation was driven by the oxidation of a tertiary amine. Solvent played a critical role in the photoredox cyclization outcome, whereas methanol led to a mixed ketal, acetonitrile/water (10:1) gave direct cyclization to (±)-tetrabenazine and occurred more rapidly.

| S-EPMC4684717 | biostudies-literature

Characterizing Chain Processes in Visible Light Photoredox Catalysis.

Project description:The recognition that Ru(bpy)32+ andsimilar visible light absorbing transition metal complexes can be photocatalysts for a variety of synthetically useful organic reactions has resulted in a recent resurgence of interest in photoredox catalysis. However, many of the critical mechanistic aspects of this class of reactions remain poorly understood. In particular, the degree to which visible light photoredox reactions involve radical chain processes has been a point of some disagreement that has not been subjected to systematic analysis. We have now performed quantum yield measurements to demonstrate that threerepresentative, mechanistically distinct photoredox processes involve product-forming chain reactions. Moreover, we show that the combination of quantum yield and luminescence quenching experiments provides a rapid method to estimate the length of these chains. Together, these measurements constitute a robust, operationally facile strategy for characterizing chain processes in a wide range of visible light photoredox reactions.

| S-EPMC4676763 | biostudies-literature

Divergent ring-opening coupling between cyclopropanols and alkynes under cobalt catalysis.

Project description:Cobalt-diphosphine catalysts promote ring-opening coupling reactions between cyclopropanols and unactivated internal alkynes, affording either ?-alkenyl ketones or multisubstituted cyclopentenol derivatives in good yields with good to excellent regioselectivities. The chemoselectivity between these ?-alkenylation and [3 + 2] annulation reactions, which likely share a cobalt homoenolate as a key catalytic intermediate, is exquisitely controlled by the reaction conditions, with the solvent being a major controlling factor. The reactions are proposed to involve ring opening of cobalt cyclopropoxide into homoenolate, migratory insertion of the alkyne into the Co-C bond, and protodemetalation or intramolecular carbonyl addition of the resulting alkenylcobalt species. The feasibility of these reaction steps was supported by DFT calculations.

| S-EPMC6124909 | biostudies-other

Naphthalene diimides with improved solubility for visible light photoredox catalysis.

Project description:Five core-substituted naphthalene diimides bearing two dialkylamino groups were synthesized as potential visible light photoredox catalysts and characterized by methods of optical spectroscopy and electrochemistry in comparison with one unsubstituted naphthalene diimide as reference. The core-substituted naphthalene diimides differ by the alkyl groups at the imide nitrogens and at the nitrogens of the two substituents at the core in order to enhance their solubility in DMF and thereby enhance their photoredox catalytic potential. The 1-ethylpropyl group as rather short and branched alkyl substituent at the imide nitrogen and the n-propyl group as short and unbranched one at the core amines yielded the best solubilities. The electron-donating diaminoalkyl substituents together with the electron-deficient aromatic core of the naphthalene diimides increase the charge-transfer character of their photoexcited states and thus shift their absorption into the visible light (500-650 nm). The excited state reduction potential was estimated to be approximately +1.0 V (vs SCE) which is sufficient to photocatalyze typical organic reactions. The photoredox catalytic activity in the visible light range was tested by the ?-alkylation of 1-octanal as benchmark reaction. Irradiations were performed with LEDs in the visible light range between 520 nm and 640 nm. The irradiation by visible light together with the use of an organic dye instead of a transition metal complex as photoredox catalyst improve the sustainability and make photoredox catalysis "greener".

| S-EPMC6720061 | biostudies-literature

Visible-light photoredox catalysis enabled bromination of phenols and alkenes.

Project description:A mild and efficient methodology for the bromination of phenols and alkenes has been developed utilizing visible light-induced photoredox catalysis. The bromine was generated in situ from the oxidation of Br(-) by Ru(bpy)3 (3+), both of which resulted from the oxidative quenching process.

| S-EPMC3999835 | biostudies-literature

Cobalt-catalyzed aminocarbonylation of (hetero)aryl halides promoted by visible light.

Project description:The catalytic aminocarbonylation of (hetero)aryl halides is widely applied in the synthesis of amides but relies heavily on the use of precious metal catalysis. Herein, we report an aminocarbonylation of (hetero)aryl halides using a simple cobalt catalyst under visible light irradiation. The reaction extends to the use of (hetero)aryl chlorides and is successful with a broad range of amine nucleophiles. Mechanistic investigations are consistent with a reaction proceeding via intermolecular charge transfer involving a donor-acceptor complex of the substrate and cobaltate catalyst.

| S-EPMC8159399 | biostudies-literature

Alcohol Etherification via Alkoxy Radicals Generated by Visible-Light Photoredox Catalysis.

Project description:A mechanistically divergent method is described that, employing a commercially available hypervalent iodine(III) reagent, generates alkoxy radicals from 1°, 2°, and 3° alcohols and allows their use in the functionalization of C(sp3)-H and C(sp2)-H bonds. This visible-light photoredox catalysis produces alkyl ethers via 1,5/6-hydrogen atom transfer or aryl ethers via 1,5-addition. This mild methodology provides a practical strategy for the synthesis of acetals, orthoesters, tetrahydrofurans, and chromanes.

| S-EPMC7653678 | biostudies-literature

Efficient visible-light photocatalytic degradation system assisted by conventional Pd catalysis.

Project description:Different approaches like doping and sensitization have been used to develop photocatalysts that can lead to high reactivity under visible-light illumination, which would allow efficient utilization of solar irradiation and even interior lighting. We demonstrated a conceptually different approach by changing reaction route via introducing the idea of conventional Pd catalysis used in cross-coupling reactions into photocatalysis. The -O-Pd-Cl surface species modified on Ni-doped TiO2 can play a role the same as that in chemical catalysis, resulting in remarkably enhanced photocatalytic activity under visible-light irradiation. For instance, Pd/Ni-TiO2 has much higher activity than N-TiO2 (about 3 ~ 9 times for all of the 4-XP systems) upon irradiation with wavelength of 420 nm. The catalytically active Pd(0) is achieved by reduction of photogenerated electrons from Ni-TiO2. Given high efficient, stable Pd catalysts or other suitable chemical catalysts, this concept may enable realization of the practical applications of photocatalysis.

| S-EPMC5380333 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data